Meta-phenoxybenzyl esters and .alpha.-cyano-m-phenoxybenzyl esters of 2-haloalkyl(oxy-, thio-, sulfinyl-, or sulfonyl)-phenylalkanoic acids are known insecticidal and acaricidal agents. These compounds and methods for their preparation are disclosed in Berkelhammer et al., U.S. Pat. Nos. 4,178,460 and 4,199,595. In both Berkelhammer et al., U.S. Pat. Nos. 4,178,460 and 4,199,595, there is disclosed the conversion of certain .alpha.-alkyl-3(or 4)-hydroxyphenylacetic acids having the formula ##STR3## wherein R is ethyl, n-propyl or isopropyl to the corresponding .alpha.-alkyl-3(or 4)-difluoromethoxyphenylacetic acids having the formula ##STR4## wherein R is as defined above by treatment with chlorodifluoromethane in aqueous alkali and dioxane. The .alpha.-alkyl-3(or 4)-difluoromethoxyphenylacetic acids thus formed can then be treated with thionyl chloride, thionyl bromide, or the like, preferably in the presence of an aromatic solvent such as benzene or toluene, to yield .alpha.-alkyl(substituted phenyl)acetyl halide which is reacted with m-phenoxybenzyl alcohol or .alpha.-cyano-m-phenoxybenzyl alcohol to yield the desired m-phenoxybenzyl ester or .alpha.-cyano-m-phenoxybenzyl ester of the 2-haloalkyl(oxy-, thio-, sulfinyl- or sulfonyl)phenylalkanoic acids which are useful insecticides. In Berkelhammer et al., U.S. Pat. Nos. 4,178,460 and 4,199,595, .alpha.-alkyl-3(or 4)-hydroxyphenylacetic acid intermediates are prepared by reacting the appropriate .alpha.-alkyl-3(or 4)-methoxyphenylacetonitrile with hydrobromic acid.
A new process for the synthesis of .alpha.-hydrocarbyl-4-hydroxyphenylacetic acids now has been discovered in which these materials can be prepared in a simple and straight-forward manner. In this new process, 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenols are produced in a novel synthesis reaction and are used as intermediates in a reaction sequence in which .alpha.-hydrocarbyl-4-hydroxyphenylacetic acids are likewise produced and used as reaction intermediates.
Methods are known for preparing 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenols. For example, the preparation of 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-disubstituted phenol by reacting .alpha.-alkyl-4-hydroxy-3,5-di-t-butylbenzyl halides with sodium cyanide is reported by A. A. Volod'kin et al., Iz. Akad. Nauk. SSSR. Ser. Khim, 1966, 1031. Also, the preparation of 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenol by the electrochemical reduction of the corresponding 2,6-di-substituted methylene-quinones is reported by L. I. Kudinova, et al., Iz. Akad. Nauk. SSSR, Ser. Khim, 1978, 1313. In U.S. application Ser. No. 385,610, entitled "Method of Preparing 4-(.alpha.-Alkyl-.alpha.-Cyanomethyl)2,6-Di-Substituted Phenol", filed on June 7, 1982, now U.S. Pat. No. 4,405,528, there is disclosed a novel process for the synthesis of 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenol by reacting a 2,6-di-substituted phenol with a Friedel-Crafts addition agent in the presence of a Friedel-Crafts catalyst such as aluminum chloride to form the corresponding 4-(.alpha.-alkyl-.alpha.-oxomethyl)2,6-di-substituted phenol, reducing the 4-(.alpha.-alkyl-.alpha.-oxomethyl)2,6 -di-substituted phenol to form the corresponding 4-(.alpha.-alkyl-.alpha.-hydroxymethyl)2,6-di-substituted phenol and thereafter reacting the 4-(.alpha.-alkyl-.alpha.-hydroxymethyl)2,6-di-substituted phenol with an alkali metal cyanide or an alkaline earth metal cyanide to form the desired 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenol.
In U.S. application Ser. No. 385,609, entitled "Preparation of 4-(.alpha.-Alkyl-.alpha.-Cyanomethyl)2,6-Di-Substituted Phenol" filed on June 7, 1982, now abandoned, there is disclosed a novel process for the synthesis of 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenol by reacting a 2,6-di-substituted phenol with an aliphatic aldehyde and an alkali metal cyanide or an alkaline earth metal cyanide in a suitable reaction solvent to form the corresponding 4-(.alpha.-alkyl-.alpha.-cyanomethyl)2,6-di-substituted phenol. And, in U.S. application Ser. No. 515,645, entitled "Method of Preparing 4-(.alpha.-Hydrocarbyl-.alpha.-Cyanomethyl)2,6-Di-Substituted Phenols," filed on July 20, 1983, there is disclosed a novel process for the synthesis of 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-hydrocarbyl-substituted phenols by reacting an N,N-di-hydrocarbyl-4-(.alpha.-hydrocarbyl-.alpha.-aminomethyl)2,6-di-hydro carbyl-substituted phenol with an alkali metal cyanide or an alkaline earth metal cyanide in a suitable solvent.
The synthesis of o- and p-hydroxy substituted phenylacetonitriles also is known and is reported in the literature. See, for example, Journal of Organic Chemistry, Vol. 41, No. 14, 2502 (1976).